Aliphatic tri-olefinic halides

ABSTRACT

Aliphatic hydrocarbon tri-olefinic and substituted aliphatic diolefinic halides, and derivatives thereof, intermediates therefor, syntheses thereof, and the control of insects.

United States Patent Henrick et a1.

ALIPHATIC TRl-OLEFINIC HALIDES Inventors: Clive A. Henrick; John B. Siddall,

both of Palo Alto, Calif.

Assignee: Zoecon Corporation, Palo Alto,

Calif.

Filed: Jan. 14, 1972 Appl. No.: 217,930

Related US. Application Data [1.5. CI 260/653.3; 260/611 A; 260/611 R; 260/612 D; 260/614; 260/633; 260/654 R; 424/312; 424/339; 424/340; 424/342;

[ June 17, 1975 [51] Int. Cl. C07c 21/18 [58] Field of Search 260/654 R, 653.3

[56] References Cited FOREIGN PATENTS OR APPLICATIONS 233,538 5/1964 Austria 260/654 R OTHER PUBLICATIONS Borkovec, Insect Chemosterilants, pp. 61 (1966).

Primary ExaminerDe1bert E. Gantz Assistant Examiner.1oseph A. Boska Attorney, Agent, or Firm-Donald W. Erickson [57] ABSTRACT Aliphatic hydrocarbon tri-olefinic and substituted aliphatic di-olefinic halides, and derivatives thereof, intermediates therefor, syntheses thereof, and the control of insects.

7 Claims, No Drawings ALIPHATIC TRI-OLEFINIC HALIDES This is a continuation-in-part of application Ser. No. 187,897, filed Oct. 8, 1971, now U.S. Pat. No. 3,755,411, which is a continuation-in-part of applications, Ser. No. 111,650, filed Feb. 1, 1971, now U.S. Pat. No. 3,729,486, Ser. No. 111,702, filed Feb. 1, 1971, now abandoned, Ser. No. 111,765, filed Feb. 1, 1971, now abandoned, Ser. No. 1 11,766, filed Feb. 1, 1971, now abandoned, Ser. No. 111,770, filed Feb. 1, 1971, now abandoned, and Ser. No. 1 15,725, filed Feb. 16, 1971, now U.S. Pat. No. 3,706,733, the entire disclosures of which are incorporated by reference.

This invention relates to novel aliphatic di-olefinic compounds, aliphatic tri-olefinic compounds, intermediates therefor, syntheses thereof, and the control of insects. More particularly, the novel di-olefinic compounds of the present invention are represented by the following formula:

1O els of the order of 0.001 g. to 25.0 pg. per insect. Suitable carrier substances include liquid or solid carriers, such as water, acetone, xylene, mineral or vegetable oils, talc, vermiculite, natural and synthetic resins and silica. Treatment of insects in accordance with the present invention is accomplished by spraying, dusting or exposing the insects to the vapor of the compounds of formula A. Generally, a concentration of less than 25% of the active compound is employed. The formulations can include insect attractants, emulsifying agents l l R f (I) (CH CH CH (Cl-1 C C C CH CH X (A) wherein: or wetting agents to assist in the application and effec- X is bromo, chloro, fluoro or iodo;

Z is bromo, chloro, fluoro or the group -OR in which R is hydrogen, carboxylic acyl, lower alkyl, cycloalkyl, aralkyl or aryl;

Z is hydrogen, bromo, chloro or fluoro;

each of m and n is O or the positive integer l, 2 or 3;

each of R and R is lower alkyl;

R is alkyl; and

each of R R", R and R is hydrogen or lower a1- The compounds of formula A are useful for the contiveness of the active ingredient. In the application of 30 the compounds, there is generally employed a mixture of the C-2,3 trans and cis isomers.

In the description hereinafter, each of R-R, R -R In another embodiment of the present invention, there is provided compounds of the following formula B which are useful for the control of insects in the same manner as the diolefinic compounds of formula A and trol of insects. The utility of these compounds as insect 40 hi h lso serve as precursors for the preparation of control agents is believed to be attributable to their juthe immature insect, namely during the embryo, larvae or pupae stage in view of their effect on metamorthe compounds of formula A.

i c-c=cH-cH -x (B) 50 formula C and C by halogenation:

Suitable halogenation methods include the reaction of the allylic alcohol with a halogenation agent, such as a phosphorus trihalide or phosphorus pentahalide in an organic solvent inert to the reaction. Other suitable procedures include conversion of the allylic alcohol into the respective tosylate or mesylate followed by treatment with an alkali halide, such as lithium bromide, lithium iodide, lithium chloride, sodium iodide, sodium bromide, and the like, to prepare the respective halide. The fluorides can be prepared by reaction of an iodide or bromide with silver fluoride.

The allylic alcohols can be prepared by the reduction of an a,B-unsaturated acid or ester of formula B using lithium aluminum hydride and the like, in an organic solvent inert to the reaction. The acids and esters of R R R R l I R :3 ('3 (CI-l CH CH (CH C- C C CH C 0R wherein R is hydrogen or lower alkyl.

The allylic bromides, chlorides, and iodides of formulas A and B are useful also as intermediates for the preparation of primary, secondary and tertiary amines which, in turn, are useful for the control of insects as described in application Ser. No. 187,897, US. Pat. No. 3,755,411 and application Ser. No. 217,297, filed on or about Jan. 12, 1972, now US. Pat. No. 3,839,452.

The compounds of formula A wherein Z is hydrogen and Z is halo can be prepared by treating a compound of formula B with hydrogen halide in an organic solvent such as carbon tetrachloride or other halogenated hydrocarbon solvents of low dielectric constant. The compounds of formula A wherein Z is halo can be prepared by treating a compound of formula B with bromine, chlorine or fluorine in a halogenated hydrocarbon solvent.

The compounds of formula A wherein Z is hydrogen and Z is the group OR in which R is hydrogen can be prepared by the addition of water to the terminal olefinic bond of a compound of formula B using a mercuric salt followed by reduction of the oxymercurial intermidiate in situ. Suitable mercuric salts include mercuric acetate, mercuric nitrate, mercuric trifiuoroacetate, mercuric acylates and mercuric halides. Suitable reducing agents include the borohydrides, hydrazine and sodium amalgam. See Brown and Rei, J. Am. Chem Soc. 91, 5646 (1969); Brown et al., J. Am. Chem. Soc. 89, 1522 and 1524 (1967); and Wakabayashi, J. Med. Chem. 12, 191 (Jar'1., 1969). By conducting the reaction in the presence of an alcohol (ROl-l) such as methanol, ethanol, isopropyl alcohol, benzyl alcohol, cyclopentanol, and the like, the corresponding ether is prepared. The compounds of formula A wherein Z is OR in which R is carboxylic acyl and Z is hydrogen can be prepared from a compound of formula A wherein Z is OH and Z is hydrogen by reaction with a carboxylic acid chloride or bromide or carboxylic acid anhydride in pyridine or by treatment with a carboxylic acid anhydride in the presence of sodium acetate. The reaction is generally conducted at about room temperature to reflux temperature for about 1 to 48 hours, shorter reaction time being favored by temperatures above room temperature.

The term cycloalkyl", as used herein, refers to a cyclic alkyl group of four to eight carbon atoms. The term aralkyl refers to a monovalent hydrocarbon group in which an aryl group is substituted for a hydrogen atom of an alkyl group, such as benzyl, xylyl, mesityl, phenylethyl, methylbenzyl, naphthylmethyl and naphthylethyl containing up to twelve carbon atoms. The term aryl, as used herein, refers to an aromatic group of up to twelve carbon atoms. Typical aromatic groups include phenyl, naphthyl, lower alkylphenyl such as methylphenyl, ethylphenyl, t-butylphenyl and isopropylphenyl, lower alkylthiophenyl such as methylthiophenyl, ethylthiophenyl and isopropylthiophenyl, lower alkoxyphenyl such as methoxyphenyl and ethoxyphenyl, halophenyl such as chlorophenyl, bromophenyl, iodophenyl and fluorophenyl, nitrophenyl, and lower alkenylphenyl such as vinylphenyl and allylphenyl. In the case of substituted phenyl, the substituent such as lower alkyl, lower alkythio, lower alkoxy, halo, nitro, lower alkenyl, and cyano, can be in one or more positions of the phenyl ring, usually in the para position.

The term carboxylic acyl, as used herein, refers to the acyl group of a carboxylic acid, anhydride or halide. The acyl group is determined by the particular carboxylic acid halide or carboxylic acid anhydride employed in the esterification. Although no upper limitation need be placed on the number of carbon atoms contained in the acyl group within the scope of the present invention, generally it contains from 1 to 18 carbon atoms. Typical esters of the present invention include formate, acetate, propionate, enanthate, benzoate, trimethylacetate, trichloroacetate, trifluoroacetate, t-butylacetate, phenoxyacetate, cyclopentylpropionate, aminoacetate, B-chloropropionate, adamantoate, octadec-9-enoate, dichloroacetate, butyrate, pentanoate, hexanoate, phenylacetate, pmethylbenzoate, B-phenylpropionate, 3,4-dimethylbenzoate, p isopropylbenzoate, cyclohexylacetate, stearate, methacrylate, p-chloromethylbenzoate, pmethoxybenzoate and p-nitrobenzoate.

The term alkyl refers to a branched or straight chain, saturated aliphatic hydrocarbon of 1 to 12 carbon atoms. The term lower alkyl refers to an alkyl group having a chain length of l to 6 carbon atoms.

The presence of an olefinic bond at position C-2 and C-4 of the compounds of formula A give rise to four isomers, each of which is embraced by the present invention. The presence of three olefinic bonds in compounds of formula B give rise to eight isomers, each of which is embraced by the present invention. As mentioned above, a mixture of isomers is suitably employed for the control of insects such as a mixture containing the trans (2), trans (4) isomer and the cis (2), trans (4) isomer. The conditions of the syntheses described herein and the reactants can be selected so as to favor formation of one isomer such as the all trans isomer over the formation of other isomers. The selection of isomers which, if desired, can be separated using known separation methods. Hereafter, when only one designation of configuration is given, the designation refers to position C-2,3 and the configuration is taken to be trans at position C-4,5 when not otherwise specified. The use of trans/cis and cis/trans is with reference to position C-2,3 and indicates a mixture of isomers.

The following examples are provided to illustrate the practice of the present invention. Temperature is given in degrees Centigrade.

EXAMPLE 1 To a mixture of one g. of 3,7-dimethyloct-6-en-1-al 1.5 g. of phosphonate (II; R is ethyl, R is methyl, R is ethoxy, R is hydrogen) and 50 ml. of dimethylformamide, under nitrogen, is slowly added sodium ethoxide (prepared from 200 mg. of sodium and 12 ml. of ethanol). The mixture is allowed to stand at room temperature for one hour and then is worked up with ether. The ethereal extracts are dried, concentrated and then chromatographed on silica plates eluting with hexane/ether to yield ethyl 3,7,1 1-trimethyldodeca-2,4,10- trienoate which is predominantly trans at position C-2,3 and 04,5.

By using diethyl 3-methoxycarbonyl-2-methylprop-2- enyl phosphonate and sodium methoxide, there is prepared methyl 3,7,1 1-trimethyldodeca-2,4, 1 O-trienoate.

EXAMPLE 2 The process of Example 1 is repeated using each of the aldehydes under column 1 as the starting material to yield the respective ester under column 11 3 7-dimethylnon-6-en- 1 -al 3-ethyl-7-methylnon-6-en- 1 -al 3 ,7-diethylnon-6-en- 1 -al 4,8-dimethylnon-7-en-1-al 3 ,6-dimethylhept-5-en- 1 -al 3 ,6-dimethyloct-5-en- 1 -al 2 ,6-dimethylhept-5-en- 1 -al ethyl 3 ,7 ,1 1-trimethyltrideca-2,4,10-trienoate ethyl 3,1 1-dimethyl-7-ethyltrideca-2,4,10-trienoate ethyl 7,1 l-diethyl-3-methyltrideca 2,4,10-trienoate ethyl 3,8, l2-triemthyltrideca-2,4,l l-trienoate ethyl 3,7,l0-trimethylundeca-2,4,9-trienoate ethyl 3,7,10-trimethyldodeca-2,4,9-trienoate ethyl 3,6,l0-trimethylundeca-2,4,9-trienoate EXAMPLE 3 A mixture of 1 g. of trans/cis methyl 3,7,11- trimethyldodeca-2,4,lO-trienoate. 60 ml. of methanol, 0.5 g. of potassium hydroxide and 6 ml. of water is heated at reflux for about 8 hours. The mixture is then diluted with water, neutralized and extracted with ether. The organic phase is washed with water, dried over sodium sulfate and evaporated to yield trans/cis 3,7,1 l-trimethyldodeca-2,4, IO-trienoic acid.

Using the foregoing procedure, the other esters of Example 2 are hydrolyzed to produce the respective free acids under column 111.

Ill

3 ,7 ,1 1-trimethyltrideca-2,4- 1 O-trienoic acid 3 ,1 1-dimethyl-7-ethyltrideca-2,4, 1 O-trienoic acid 7,1 1-diethyl-3-methyltrideca-2,4,l0-trienoic acid 3,8 1 2-trimethyltrideca-2,4,l l-trienoic acid 3,7,10-trimethylundeca-Z,4,9-trienoic acid 3 ,7,10-trimethyldodeca-Z,4,9-trienoic acid 3,6,10-trimethylundeca-2,4,9-trienoic acid EXAMPLE 4 One gram of thionyl chloride is added with stirring at room temperature to 0.5 g. of trans/cis 3,7,l1-trimethyldodeca-2,4,10-trienoic acid and the mixture heated at about 50 for 10 minutes. Excess thionyl chloride is removed by evaporation and then t-butyl alcohol (about 2 equivalents) is added and the mixture heated at about 50 for about 5 minutes to yield t-butyl 3,7,1 1 trimethyldodeca-2,4, 1 O-trienoate (trans/cis).

By using other alcohols in place of t-butyl alcohol in the process of this Example, such as cyclohexyl alcohol, isopropyl alcohol, benzyl alcohol, n-pentanol, nhexanol, or n-propanol, the respective esters are prepared, i.e.,

cyclohexyl 3,7,1 1-trimethyldodeca-2,4,10-trienoate isopropyl 3,7, 1 1-trimethyldodeca-2,4, 1 O-trienoate benzyl 3,7,1 l-trimethyldodeca-2,4, 1 O-trienoate n-pentyl 3,7,1 1-trimethy1dodeca-2,4,10-trienoate n-hexyl 3 ,7, l l-trimethyldodeca-2,4, lO-trienoate n-propyl 3,7,1 1-trimethyldodeca-2,4, 1 O-trienoate EXAMPLE 5 To a solution of 0.5 g. of trans/cis 3,7,l1-trimethyldodeca-2,4,10-trienoic acid in 15 ml. of benzene is added with stirring an equivalent amount of potassium bicarbonate. The mixture is stirred until the evolution of carbon dioxide ceases and then evaporated to yield potassium 3,7 ,1 1-trimethyldodeca-2,4, l O-trienoate.

Alternatively, acid salts can be prepared by titrating the acid with an organic solution or aqueous organic solution of the desired metal.

EXAMPLE 6 One gram of 3,7,1l-trimethyltrideca-2,4,IO-trienoic acid in 30 ml. of benzene and one mol of sodium hydride is stirred about 2 hours and then a slight excess of oxalyl chloride is added at about 0 and stirred for 1 hour. The product is worked up by removal of solvent in vacuo and extraction with pentane to yield 3,7,11- trimethyltrideca-2,4, 1 O-trienoyl chloride.

EXAMPLE 7 A. to magnesium propynylide (15 g.) in 150 ml. of ether is slowly added 0.3 moles of 3,7-dimethyloct-6- en-l-al and the mixture then stirred overnight. Saturated aqueous ammonium chloride is added and the layers separated. The organic phase, combined with ether backwashings of aqueous phase, is washed with water, dried and solvent evaporated to yield 6,10- dimethyl-9-undecen-2-yn-4-ol which can be purified by chromatography.

B. A mixture of 18.5 g. of the alkynyl alcohol of part A, g. of triethylorthoacetate and 0.7 g. of propionic acid is refluxed under a spinning band column to remove ethanol as it is formed. After the elimination of EXAMPLE 8 The process of Example 7, part A, is repeated using each of the aldehydes under columnn l as the starting material to yield the respective alkynyl alcohol under column lV, each of which is reacted with triethylorthoacetate using the process of Example 7, part B, to prepare the respective allenic ester under column V.

6,10-dimethyl-9-dodecen-2-yn-4-ol 6-methy1-l0-ethyl-9-dodecen-2-yn-4-ol 6 ,10-diethyl-9-dodecen-2-yn-4-ol 7,1 1 -dimethyl- 1 O-dodecen-2-yn-4-ol 6,9-dimethyl-8-decen-2-yn-4-ol 6 ,9-dimethyl-8-undecen-2-yn-4-ol 5,9-dimethyl-8-decen-2-ym4-ol ethyl 3 ,7 ,1 1-trimethyltrideca-3 ,4, 1 O-trienoate ethyl 3,1 1-dimethyl-7-ethyltrideca-3,4,IO-trienoate ethyl 3-methyl-7 ,1 1-diethyltrideca-3 ,4, l O-trienoate ethyl 3,8,l2-trimethyltrideca-3,4,l l-trienoate ethyl 3 ,7 ,10-trimethylundeca-3 ,4,9-trienoate ethyl 3 ,7 lO-trimethyldodeca-3 ,4,9-trienoate ethyl 3,6,10-trimethylundeca-3,4,9-trienoate using the process of Example 7, part C, each of the allenic esters under column V is rearranged by treatment with aqueous sodium hydroxide to produce the respective a, B-unsaturated ester.

EXAMPLE 9 To 126 mg. of a 57% dispersion of sodium hydride in oil is added pentane. The pentane is removed and the sodium hydride washed several times with pentane. To the washed sodium hydride is added 582 mg. of diethyl acetyl-methylphosphonate (IIA; R is ethyl, R is methyl, R is hydrogen) in m1. of tetrahydrofuran at under argon. After several minutes, the solution is transferred to a solution of 425 mg. of 3,7-dimethy1oct-6-en-1-al in about 4 ml. of dry tetrahydrofuran under argon over a period of about 20 minutes at room temperature. After about two hours, water is added followed by addition of ether and the layers separated. The organic layer is washed with saturated sodium chloride, dried over sodium sulfate and evaporated under reduced pressure to yield 6,10-dimethylundeca- 3,9-dien-2-one.

EXAMPLE 10 One gram of triphenylphosphineacetylmethylene and 425 mg. of 3,7-dimethylnon-6-en-l-al are dissolved in 10 ml. toluene and refluxed under nitrogen overnight. The toluene is distilled off and the formed triphenylphosphine oxide crystallized by addition of pentane. Filtration and evaporation of the pentane gives a residue, which is further purified by preparative thin layer chromatography to yield 6,10-dimethyldodeca-3,9- dien-2-one.

EXAMPLE 1 1 41 Grams of 3,7-dimethyloct-6-en-1-al and g. of recrystallized (ethyl acetate) triphenylphosphineacetyl-methylene [Ramirez et al., J. Org. Chem. 22, 41 (1957) are refluxed in one liter of dry toluene for 18 hours, under nitrogen. Most of the solvent is removed in vacuo, 500 ml. pentane is added and the mixture filtered. The flask and the triphenylphosphine oxide filter cake are washed several times with pentane. The filtrate is concentrated under vacuum to yield 6,10- dimethylundeca-3,9-diene-2-one.

EXAMPLE 12 Using the process of either of Example 9, 10 or 11, each of the aldehydes under column I is converted into the respective di-unsaturated ketone undercolumn VI.

6,10-dimethyldodeca-3,9-dien-2-one 6-methyl-10-ethyldodeca-3 ,9-dien-2-one 6, lO-diethyldodeca-3,9-dieri-2-one 7,1 1-dimethyldodeca-3, 1 O-dien-Z-one 6,9-dimethyldeca-3,8-dien-2-one 6,9-dimethy1undeca-3,8-dien-2-one 5,9-dimethyldeca-3,8-dien-2-one EXAMPLE 13 The carbanion of diethyl carbomethoxymethyl phosphonate is reacted with 6,10-dimethylundeca-3,9- dien 12-one-dien-each of the ketones under column Vl using the procedure of either Example 1 or 9 to prepare .the respective methyl esters under column VII.

VII

methyl 3,7 ,1 l-trimethyld odeca-2,4, 1 O-trienoate methyl 3 ,7 ,1 1-trimethyltrideca-2,4,IO-trienoate methyl 3,1 l-dimethyl -7-ethyltrideca-2,4,10-

trienoate methyl 3-methyl-7,'l l-diethyltrideca-2,4,10-

trienoate methyl 3 ,8, l 2-trimethyltrideca-2,4,-1 l-trienoate methyl 3,7,10-trimethylundeca-2,4,9-trienoate methyl 3,7,10-trimethyldodeca-2,4,9-trienoate. methyl 3,6,1O -trimethyIundeca-Z,4,9-trienoate EXAMPLE l4 ethyl l l-chloro-3,7,1 l-trimethyltrideca-2,4-

dienoate, ethyl l l-chloro-3,1-l-dimethyl-7-ethyltrideca-2,4- dienoate,

ethyl 1 1-chloro-7,l 1-diethyl-Bmethyltrideca-2,4-

' dienoate, 1 l 3 ethyl l2-chloro-3,8,12-trimethyltrideca-2,4-

dienoate,

ethyl 10-ch1oro-3,7,10-trimethylundeca-2,4-

dienoate,

ethyl 10-chloro-3 ,7 ,10-trimethyldodeca-2,4-

dienoate, and

ethyl l0-chloro-3 ,6, 1 O-trimethylundeca-2,4-

dienoate.

Each of the esters under col. VII is used as the starting material in the process of this example to prepare the hydrochlorides under col. IX.

trienoate, cyclohexyl 3,7,1 1-trimethyldodeca-2,4,10- trienoate and n-hexyl 3,7,10-trimethylundeca-2,4,9- trienoate is used as the starting material in the procedure of Example 14 to prepare the respective compound, that is benzyl 1 1-chloro-3,7,l 1-trimethyltrideca-2,4-

dienoate,

isopropyl l 1-chloro-3,7,l l-trimethyldodeca-2,4-

dienoate,

cyclohexyl 1 1-chloro-3,7,1 1-trimethyldodeca-2,4-

dienoate, and

n-hexyl l0-chloro-3 ,7,10-trimethylundeca-2,4-

dienoate.

EXAMPLE 16 One gram of trans ethyl 3,7,1 l-trimethyldodeca- 2,4,1 O-trienoate is added to a solution of 1 equiv. of dry hydrogenfluoride in dry tetrahydrofuran. The mixture is allowed to stand at 0 for hours and is then washed with water, dried and evaporated under reduced pressure to yield trans ethyl l 1-f1uoro-3,7,l l-trimethyldodeca-2,4-dienoate which can be purified by chromatography.

EXAMPLE 17 The process of Example 14 is repeated with the exception of using dry hydrogen bromide in place of hydrogen chloride to yield trans ethyl l l-bromo-3,7,1 1- trimethyldodeca-Z,4-dienoate.

By treating the 1 l-bromide with anhydrous silver fluoride in acetonitrile under reflux conditions for about 6 hours, there is prepared trans ethyl l 1-fluoro-3,7,1 ltrimethyldodeca-2,4-dienoate.

EXAMPLE 18 Chlorine gas is bubbled into 200 ml. of carbon tetrachloride at 0 until one equivalent is taken up. Twentyfive grams of trans ethyl 3,7,1 l-trimethyldodeca- 2,4,10-trienoate is added and the mixture is then stirred and then allowed to stant at about 0 for 24 hours. The mixture is then evaporated to yield trans ethyl 10,11- dichloro-3,7,l 1-trimethyldodeca-2,4-dienoate which can be purified by chromatography.

EXAMPLE 19 To a mixture of 5 g. of trans ethyl 3,7,11-trimethyldodeca-2,4,10-trienoate in ml. of fluorotrichloromethane is slowly added 1 equiv. of dry fluorine is about 1 hour at about -7 8. After stirring the mixture at this temperature for about 16 hours, the resultant mixture is evaporated and chromatographed on silica to yield trans ethyl 10,11-difluoro-3,7,ll-trimethyldodeca-2,4-dienoate.

By using bromine in the process of Example 18 there is prepared trans ethyl 10,11-dibromo-3,7,11- trimethyldodeca-2,4-dienoate.

EXAMPLE 20 To a mixture of 1.9 g. of mercuric acetate, 6 ml. of water and 20 ml. of tetrahydrofuran is added 1.49 g. of trans ethyl 3,7,1 1-trimethyldodeca-2,4,10-trienoate slowly. After addition is complete, the reaction mixture is stirred for about 20 minutes. The mixture is cooled to about 0 and 6 ml. of aqueous sodium hydroxide (3molar) is added followed by 0.49 g. of sodium borohydride in aqueous sodium hydroxide (about 3 molar). The mixture is stirred for about 30 minutes. The mixture is then decanted, concentrated, diluted with water and then extracted with ether. The ethereal extract is washed with water, dried over magnesium sulfate and the product chromatographed on silica gives ethyl 11- hydroxy-3,7,1 1-trimethyldodeca-2,4-dienoate (trans).

The above process is repeated using each of the unsaturated esters under Column II to prepare the respective compound under Column X.

dienoate, and ethyl 10-hydroxy-3 ,6, 1 0-trimethylundeca-2 ,4-

dienoate.

EXAMPLE 21 Each of the esters under Column VII is used as the starting material in the process of Example 20 to prepare the respective hydroxyl under Column X1:

methyl 1 1-hydroxy-3,7,1 l-trimethyldodeca-2,4-

dienoate,

methyl 1 l-hydroxy-3,7,l l-trimethyltrideca-2,4-

dienoate, methyl 1 l-hydroxy-3,l 1-dimethyl-7-ethyltrideca- 2,4-dienoate, methyl 1 l-hydroxy-3-methyl-7,l l-diethyltrideca- 2,4-dienoate, methyl l2-hydroxy-3 ,8 l 2-trimethyltrideca-2 ,4-

dienoate, methyl 10-hydroxy3,7,l0-trimethylundeca-2,4-

dienoate. methyl 10-hydroxy-3,7,l0-trimethyldodeca-2,4-

dienoate, and methyl lO-hydroxy-3,6, l -trimethylundeca-2,4-

dienoate.

EXAMPLE 22 Each of benzyl 3,7,1l-trimethyltrideca-2,4,10- trienoate, isopropyl 3 ,7,1 1-trimethyldodeca-2,4,10-

trienoate, cyclohexyl 3,7,1 l-trimethyld0deca-2,4,lO- trienoate and n-hexyl 3,7,lO-trirnethylundeca-2,4,9- trienoate is used as the starting material in the process of Example 20 to prepare the respective hydroxy, that benzyl 1 l-hydroxy-3,7,l l-trimethyltrideca-2,4-

dienoate,

isopropyl l l-hydroxy-3,7,l 1-trimethyldodeca2,4-

dienoate,

cyclohexyl l l-hydroxy-3,7,l l-trimethyldodeca-2,4-

dienoate, and

n-hexyl -hydroxy-3 ,7, l 0trimethylundeca-2,4-

dienoate.

EXAMPLE 23 To a solution of 2 g. of trans ethyl 3,7,1 l-trimethyldodeca-2,4,l0-trienoate in 20 ml. of ethanol, cooled to 0 in an ice bath, is added a suspension of 2.32 g. of mercuric acetate in 50 ml. of ethanol over minutes. The reaction mixture is stirred for 2 hours and then, with cooling, 1.22 g. of potassium hydroxide in ml. of ethanol is added. Then 0.139 g. of sodium borohydride is added in small portions and stirring continued for minutes. The solution is decanted, then concentrated to half volume, diluted with 100 ml. of water and extracted with ether (3 X 50). The ethereal phase is washed with water, dried over magnesum sulfate and the crude product chromatographed on silica using hexanezether to yield trans ethyl ll-ethoxy-3,7,l ltrimethyldodeca-2,4-dienoate.

EXAMPLE 24 A mixture of l g. of trans ethyl ll-hydroxy-3,7,l ltrimethyldodeca-2,4-dienoate, 10 ml. of acetic anhydride and 0.5 g. of dry sodium acetate is refluxed for about 5 hours. After cooling, excess anhydride is removed by vacuum and the residue extracted with ether. The etheral extract'is washed, dried over magnesium sulfate and evaporated to yield the corresponding acetate, trans ethyl 1 l-acetoxy-3,7,1l-trimethyldodeca- 2,4-dienoate.

EXAMPLE 25 A mixture of 2 g. of dry trans ethyl ll-hydroxy- 3,7,1l-trimethyldodeca-2,4-dienoate, 15 ml. of acetyl chloride and 20 ml. of dry pyridine under nitrogen is heated on a steam bath for about 6 hours. After cooling, the mixture is concentrated under vacuum and the residue taken up in ether. The ethereal extract is washed, dried over magnesium sulfate and evaporated to yield the corresponding acetate, trans ethyl llacetoxy-3,7,l 1-trimethyldodeca-2,4-dienoate.

The process of this example is repeated with the exception of using triethylamine in place of pyridine to yield the l l-acetate.

EXAMPLE 26 One gram of trans ethyl 1l-hydroxy-3,7,l ltrimethyldodeca-2,4-dienoate in 10 ml. of diglyme is added dropwise to a slurry of l g. of sodium hydride in 10 ml. of diglyme under nitrogen. To this mixture is added 0.9 g. of cyclohexylchloride. The reaction mixture is stirred at about 25 for 30 minutes and then quenched an ice water. The organic phase is separated and aqueous phase re-extracted with ether. The organic materials are washed with water, dried over sodium sulfate and evaporated to yield the cyclohexyl ether of trans ethyl 1 l-hydroxy-3,7,l l-trimethyldodeca 2,4-dienoate.

By using each of benzyl chloride and cyclopentyl chloride in the foregoing procedure, the corresponding benzyl ether and cyclopentyl ether is prepared.

EXAMPLE 27 By use of the procedure of Example 25, ethyl llhydroxy-3,7,ll-trimethyldodeca-2,4-dienoate is converted into the corresponding ll-chloroacetate, 11- dichloroacetate and ll-trichloroacetate using chloroacetyl chloride, dichloroacetyl chloride and trichloroacetyl chloride, respectively.

The respective ll-trifluororacetate, propionate, nbutanoate, n-pentanoate and n-hexanoate esters of ethyl 1 l-hydroxy-3 ,7,l l-trimethyldodeca-2,4-dienoate are prepared according to the process of Example 24 using trifiuoroacetic anhydride, propionic anhydride, n-butyric anhydride, n-pentanoic anhydride and nhexanoic anhydride or according to the process of Example 25 using the corresponding acid chloride.

EXAMPLE 28 A mixture of 20 ml. of dry formic acid and 2 g. of trans ethyl 3,7,1l-trimethyldodeca-2,4,10-trienoate is heated at 50 for 2 hours and then poured onto ice cold potassium bicarbonate solution. The reaction is worked up by extraction with ether, washing the ethereal extract, drying over magnesium sulfate and evaporation to yield the formate of trans ethyl ll-hydroxy-3,7,l 1- trimethyldodeca-2,4-dienoate.

Using the above process, the formates of formula A are prepared form the corresponding precursor of formula B having a terminal olefinic bond.

EXAMPLE 29 Fifteen grams of mercuric acetate in 50 ml. of dry ethanol is added to 12 g. of trans ethyl 3,7,1 1- trimethyldodeca-2,4,l0-trienoate in 30 ml. of dry ethanol cooled in an ice bath. The temperature is allowed to come to room temperature by standing overnight. Then the mixture is cooled to 0, 10 g. of potassium hydroxide in ml. of ethanol is added followed by addition of 1.0 g. of sodium borohydride in small portions. After about 30 minutes at 0, water is added and mixture left at room temperature for 2 hours. The mixture is filtered, filtrate concentrated and extracted with ether. The etheral extract is washed, dried, and evapo rated to yield trans ethyl 1l-eth0xy-3,7,l l-trimethyldodeca-2,4-dienoate which is purified by distillation or chromatography.

By using methanol in the foregoing process in place of ethanol, there is prepared the respective ll-methyl ether. In the same way, each of isopropanol, t-butanol, and n-propanol is added to the terminal double bond to prepare:

ethyl l l-isopropoxy-3,7,l l-trimethyldodeca-2,4-

dienoate, ethyl l l-t-butoxy-3 ,7,l l-trimethyldodeca-2,4-

dienoate, and ethyl l l-n-propoxy-3,7,l l-trimethyldodeca-2,4-

dienoate EXAMPLE 30 Each of the tri-unsaturated esters under col. VII is used as the starting material in the process of Example 21 or 29 to yield the respective ethoxy substituted compound under col. XII.

XII

methyl 1 I-ethoxy-3,7,I l-trimethyldodeca-2,4-

dienoate,

methyl 1 l-ethoxy-3 ,7 ,1 l-trimethyltrideca-2,4-

dienoate,

methyl II-ethoxy-3,l l-dimethyl-7-ethyltrideca-2,4-

dienoate,

methyl 1 l-ethoxy-3-methyl-7,l l-diethyltrideca-2,4-

dienoate,

methyl I 2-ethoxy-3 ,8, I 2-trimethyltrideca-2,4-

dienoate,

methyl l-ethoxy-3 ,7, I 0-trimethylundeca-2,4-

dienoate,

methyl l0-ethoxy-3 ,7 l 0-trimethyldodeca-2,4-

dienoate, and

methyl l0-ethoxy-3 ,6, I 0-trimethylundeca-2,4-

dienoate.

EXAMPLE 31 A mixture of l g. of trans methyl ll-ethoxy-3,7,l ltrimethyldodeca-2,4dienoate, 60 ml. of methanol, 0.5 g. of potassium hydroxide and 6 ml. of water is heated at reflux for about 8 hours. The mixture is then diluted with water, neutralized and extracted with ether. The organic phase is washed with water, dried over sodium sulfate and evaporated to yield trans l l-ethoxy-3,7,l ltrimethyldodeca-Z,4-dienoic acid.

EXAMPLE 32 Using each of the esters under Column II as the starting material in the process of either Example 22 or 29,

there is prepared the respective substituted ester under Column XIII.

vbutyl EXAMPLE 33 A. To a mixture of 50 g. of 7-methoxy-3,7- dimethyloctan-l-al, g. of diethyl 3-ethoxycarbonyl- 2-methylprop-2-enyl phosphonate (49% trans), and 500 ml. of dimethylformamide, under nitrogen, at 0, and with stirring, is slowly added 9 g. of sodium in 250 ml. of ethanol. After addition is complete, the reaction is allowed to continue one hour at room temperature. The reaction is worked up with hexane, filtered through Florisil and filtrate evaporated to yield trans(2), trans (4) and cis(2), trans(4) ethyl 11- methoxy-3,7,I l-trimethyldodeca-2,4-dienoate (about 60% trans, trans).

B. A mixture of 45 g. of the ethyl ester of part A, 350 ml. of ethanol, ml. of water and 70 ml. of 50% aqueous NaOH is refluxed for 22 hours. Ethanol is then removed under reduced pressure, water added followed by extraction with ether. The aqueous phase is adjusted to about pH 8 using aqueous RC1 and 31 g. of S-benzyl-isothiouronium hydrochloride in water is added. The thus-formed salt if filtered, washed with water, recrystallized from aqueous methanol (twice) and then treated with aqueous I-ICl/ether and worked up to yield 1 l-methoxy-3,7,l l-trimethyldodeca-2,4-dienoic acid which crystallizes on cooling.

C. The acid (0.5 g.) of part B is methylated using diazomethane in ether, followed by chromatography on prep. TLC and distillation (short path) to prepared methyl 1 l-methoxy-3 ,7,l l-trimethyldodeca-2,4- dienoate [95.2% trans(2), trans(4)]. In the same way, using diazoethane is prepared ethyl ll-methoxy- 3,7,1 l-trimethyldodeca-2,4-dienoate [95.2% trans(2), trans(4)].

EXAMPLE 34 To 0.5 g. of the acid of Example 33 in 10 ml. of benzene, under nitrogen, is added 0.055 g. of sodium hydride. After stirring at room temperature for 15 minutes, 0.17 ml. of oxalyl chlorideis added followed by stirring for 2.5 hours. Then 2 ml. is isopropanol is added. After about 3 hours, the reaction is worked up by extraction with ether, washing with sodium bicarbonate and brine, drying over calcium sulfate and isolation to yield isopropyl ll-methoxy-3,7,ll-trimethyldodeca-2,4-dienoate (about 91% trans, trans).

EXAMPLE 35 To 0.5 g. of the acid of Example 33 in 10 ml. of benzene, under nitrogen is added 0.17 ml. of oxalyl chloride which is stirred for about 45 minutes and then allowed to stand 2 hours. Two ml. of isopropanol is added. After 3 hours, ether is added and organic layer separated. The organic layer is washed with adqueous sodium bicarbonate and brine, dried over calcium sulfate and concentrated under reduced pressure to yield isopropyl l l-methoxy-3,7,l l-trimethyldodeca-2,4- dienoate (about 91% trans, trans) which can be purified by chromatography and distillation.

Using the foregoing precedure, each of 3- thiacyclohexanol, 2,2,2-trifluoroethanol, t-butanol, 2- methoxyethanol, 2-methylthioethanol and s-butanol provides 3 '-thiacyclohexyl l l-methoxy-3,7 ,l ltrimethyldodeca-2,4-dienoate, 2, 2', 2'-trifluoroethyl l l-methoxy-3,7,I l-trimethyldodeca-2,4-dienoate, t- I l-methoxy-3,7,l l-trimethyldodeca-2,4- dienoate. 2'-methoxyethyl l l-methoxy-3 ,7,1 ltrimethyldodeca-Z,4-dienoate, 2-methlthioethyl llmethoxy 3,7,1l-trimethyldodeca-2.4-dienoate, and s- 15 butyl l 1-methoxy-3,7,1 1-trimethy1dodeca-2,4- dienoate. Each of the esters is primarily the trans(2), trans(4) isomer.

EXAMPLE 36 Sodium ethoxide (prepared from 0.2 g. of sodium and 12 ml. of ethanol) is slowly added to a mixture of 1.1 g. of 7-ethoxy-3,7-dimethyloctan-l-al, diethyl 3- ethoxycarbonyl-2-methy1prop-2-enyl phosphate and 50 ml. of dimethylformamide, with stirring, under nitrogen, at The reaction is stirred for 1.5 hours after addition is complete and then worked up by extraction with ether to yield ethyl 11-ethoxy-3,7,1l-trimethyldodeca-2,4-dienoate, mostly trans(2), trans(4), which can be further purified by chromatograph and distillation.

EXAMPLE 37 To a mixture of g. of 7-methoxy-3,7- dimethyloctan-l-al, 17 g. of diethyl 3-ethoxycarbonyl- 2-meth1prop-2-enyl phosphonate (77% trans), and 150 ml. of dimethylformamide, under nitrogen, 0, with stirring, is added sodium isopropanolate (prepared from 1.5 g. of sodium in 150 ml. of isopropanol). After addition is complete, the reaction is stirred for 18 hours at room temperature and then worked up by extraction with hexane to yield isopropyl 1 l-methoxy-3,7,l 1- trimetyyldodeca-2,4-dienoate (mostly trans-2,trans-4), which can be chromatographed and distilled for further purification;

EXAMPLE 38 A mixture of 5 g. of hydroxycitronellal (7-hydroxy- 3,7-dimethyloctan-l-al), 8.5 g. of di-isopropyl 3- ethoxycarbonyl-2-methylprop-2-eny1 phosphanate, and 40 ml. of dimethylformamide, under nitrogen and cooled in an ice-bath, is stirred for 0.5 hour and then ground NaOH (1.165 g.) is added. The reaction mixture is stirred at room temperature for 3 hours and then hexane/water (1/1) added. The organic layer is washed with water and brine, dried over calcium sulfate and concentrated. The concentrate is filtered through Florisil using hexane and hexane/ether. The filtrate is concentrated and then distilled to yield ethyl 11- hydroxy-3 ,7,1 1-trimethyldodeca-2,4-dienoate (about 85% trans-2, trans-4).

The process of this example is repeated with the exception of using di-isopropyl 3-isopropoxycarbonyl-2- methylprop-Z-enyl phosphonate to prepare isopropyl 1 1-hydroxy-3,7,1 1-trimethyldodeca-2,4-dienoate, about 78% trans(2), trans(4) and 21% cis(2), trans(4).

EXAMPLE 39 To 40 ml. of ice cold isopropanol is added 2.49 g. of acetyl chloride. The resulting solution is stirred at 0 for min. and 1.0 g. of trans isopropyl 3,7,11- trimethyldodeca 2,4,l0-trienoate added. The solution is stirred for one hour at 0 and for 48 hours at 25. Solvent is removed under reduced pressure and the concentrate taken up in hexane. The hexane solution is washed with water until the aqueous wash is neutral and then with brine. The solution is dried over calcuim sulfate and solvent evaporated to yield trans isopropyl 1 1-chloro-3,7 ,1 1-trimethyldodeca=2,4=dienoate.

EXAMPLE 40 A. 100 Grams of 3,7=dimethyloct=6=en=1=ol is dis= solved in 150 ml. of pyridine and 100 ml. of acetic an= hydride and left at room temperature for about 48 hours. Then the mixture is extracted with ether and the ethereal extracts washed with water, 10% aqueous HCl and brine to yield 1-acetoxy-3,7-dimethy1oct-6-ene which is purified by distillation.

B. 150 Grams of mercuric acetate in 400 ml. of dry ethanol is added to g. of l-acetoxy-3,7- dimethyloct-6-ene (citronello acetate) in 200 ml. of dry ethanol cooled in an ice bath. The temperature is allowed to come to room temperature by standing overnight. Then the mixture is cooled to 0, 100 g. of potassium hydroxide in 1.5 1. of ethanol is added followed by addition of 10 g. of sodium borohydride in small portions. After about 30 minutes at 0, water (100 m1.) is added and mixture left at room temperature for 2 hours. The mixture is filtered, filtrate concentrated and extracted with ether. The ethereal extract is washed, dried and evaporated to yield 7-ethoxy-3,7- dimethyloctanl-ol which is purified by distillation or chromatography.

By using methanol in the foregoing process in place of ethanol, there is obtained 7-methoxy-3,7-dimethyloctan- 1-01.

C. A mixture of 1.9 of 7-ethoxy-3,7-dimethyloctan-1- 01 and 10 ml. of pyridine is added to a suspension of 8.0 g. of chromium trioxide in 100 ml. of pyridine with stirring under nitrogen. After about 4 hours at room temperature, the reaction is poured into saturated sodium bicarbonate and worked up with ether followed by washing with 2N NaOl-l, water, 10% l-lCl, water and brine and evaporated under reduced pressure to dryness and then filtered with hexane to yield 7-ethoxy- 3 ,7-dimethyloctan- 1 -a1.

D. A mixture of 9.0 g. of 7-ethoxy-3,7- dimethyloctan-l-al and 15 g. of triphenylphosphineacetylmethylene in 100 ml. of dry toluene, under nitrogen, is refluxed for 20 hours. Thereafter, the toluene is evaporated and pentane added to remove triphenylphosphine. After concentration, the product is distilled to yield 10-ethoxy-6,1,0-dimethylundec-3-en- 2-one. The thus-prepared ketone is reacted with the carbanion of diethyl carbethoxymethylphosphonate using the procedure of Example 1 or 9 to prepare ethyl- 1 1-ethoxy-3,7,11-trimethyldodeca-2,4-dienoate.

EXAMPLE 41 XIV 3,6,7-trimethyloct-6-en- 1 -a1 3 ,6,7-trimethylnon-6-en- 1 -a1 2,5-dimethylhex-4-en-1=al 2,4,5-trimethy1-4-en-1-al 3,5,6-trimethy1hept-5-en-l-al 2,5,6=trimethy1hept=5=en=1=a1 3 ,8-dimethy1non=7=en= 1 -al 3 9-dimethy1dec=8-en-1=al 3,7,10,11=tetrarnethyldodeca=2,4,10=

isopropyl trlenoate isopropyl 3,7,10,1 1=tetramethyltrideca=2,4,10=

trienoate isopropyl 3,6,9=trimethyldeea=2,4,8=trienoate isopropyl 3,6,8,9=tetrarnethyldeca=2,4,8=trienoate isopropyl 3.7.9.10=tetrarnethy1undeca=2,4,9=

trienoate isopropyl 3,6,9, 1 O-tetramethylundeea-2,4,9-

trienoate isopropyl 3,7,l2-trimethyltrideca-2,4,l l-trienoate isopropyl 3,7, l 3-trimethyltetradeca-2,4, l 2-trienoate The reaction of the aldehydes under col. XIV with the carbanion of diethyl 3-methoxycarbonyl-2- methylprop-2-enylphosphonate yields the respective methyl tri-unsaturated esters. In the same way the respective ethyl tri-unsaturated esters are prepared using diethyl 3-ethoxy-carbonyl-2-methylprop-2- enylphosphonate.

Hydrochlorinated derivatives of the above esters are prepared using the procedure of Example 14 or 39. For example, isopropyl-l l-chloro-3,7,l0,l l-tetramethyldodeca-2,4-dienoate, isopropyl ll-chloro-3,7,l(),l ltetramethyltrideca-2,4-dienoate, isopropyl IO-chloro- 3,7,9,lO-tetramethylundeca-2,4-dienoate, and isopropyl l2-chloro-3,7,l2-trimethyltrideca-2,4-dienoate,

Following the procedure of Example 23 or 29, methanol is added to the terminal double bond of each of the esters under col. XV to prepare:

isopropyl l l-methoxy-3,7,l0.l Ltetramethyldodeca- 2,4-dienoate,

isopropyl l l-methoxy-3,7,l(),l l-tetramethyltrideca- 2,4-dienoate,

isopropyl 9-methoxy3,6,9-trimethyldeca-2,4-

dienoate,

isopropyl 9-methoxy-3,6,8,9-tetramethyldecan-2,4-

dienoate,

isopropyl l-mcthoxy-3,7,9, l (l-tetramethylundeca- 2,4-dienoate,

isopropyl l0-methoxy-3 ,6,9, l ()-tetramethylundeca- 2,4-dicnoate,

isopropyl l2-methoxy-3 .7, l 2-trimethyltrideca-2,4-

dienoate, and

isopropyl l3-methoxy-3 ,7, l 3-trimcthyltetradeca-2,4-

dienoate.

In the same way, ethanol is added to the terminal double bond to prepare the respective ethoxy substituted 2,4-dienoates. Using the procedure of Example 20, water is added to the terminal double bond to prepare the respective hydroxy-substituted 2,4dienoate.

EXAMPLE 42 A. Eighty ml. of a 3M solution of methylmagnesium bromide in either is added slowly to 31 g. of citronellal in 250 ml. of dry ether. The mixture is heated at reflux for about 1 hour, cooled to 0 and treated with saturated aqueous ammonium chloride until reaction subsides. The organic layer is separated and the aqueous layer extracted with ether. The organic layer and ether extracts are combined, washed with water and brine and dried over magnesium sulfate. Evaporation of the solvent gives 4,8-dimethylnon-7-en-2-ol.

B. A solution of 47 g. of 4.8-dimethylnon-7-en-2-ol in 250 ml. of methylene chloride is cooled to about as a solution of 46.4 g. of sodium diehromate in 125 ml. of water is added. The mixture is maintained at about l0 as a solution of 46.3 g. of sulfuric acid in 100 ml. of water is added over about 45 minutes. The mixture is allowed to attain room temperature and. after about 3 hours, the organic layer is separated and the aqueous layer is extracted with methylene chloride. The combined organic materials are washed with saturated potassium bicarbonate. water and saturated sodium chloride, dried over magnesium sulfate and evaporated to yield 4,8-dimethynon-7-en-2-one.

The Grignard reaction of part A is repeated using each 3,7-dimethylnon-6-en-l-al, 3-methyl-7-ethylnon- 6-en- 1 -al, 3,6,7-trimethyloct-6-en- 1 -al, 3,7,8-trimethylnon-7-en- 1 -al, 2,4,5-trimethylhex-4-enl-al, 2,5-dimethylhex-4-en-l-al, 3,5,6-trimethylhept-5- en- 1 -al, 3 ,6-dimethylhept-5-en- 1 -al, 2,6-dimethylhept- S-en-l-al and 2,5,6-trimethylhept-5-en-l-al in place of citronellal to yield the respective secondary alcohol 4,8-dimthyldec-7-en-2-ol 4-methyl-8-ethyldec-7-en-2-ol 4,7,8-trimethylnon-7-en-2-ol 4,8,9-trimethyldec-8-en-2-ol 3,5,6-trimethylhept-5-en-2-ol 3,6-dimethylhept-5-en-2-ol 4,6,7-trimethyloct-6-en-2-ol 4,7-dimethyloct-6-en-2-ol 3,7-dimethyloct-6-en-2-ol 3,6,7-trimethyloct-6-en-2-ol Each of the above alcohols is oxidized to prepare the respective ketone 4,8-dimethyldec-7-en-2-one 4-methyl-8-ethyldec-7-en-2-0ne 4,7,8-trimethylnon-7-en-2-one 4,8,9-trimethyldec-8-en-2-one 3,5,6-trimethylhept-5-en-2-0ne 3,6-dimethylhept-5-en-2-one 4,6,7-trimethyloct-6-en-2-one 4,7-dimethyloct-6-en-2-one 3,7-dimethyloct-6-en-2-one 3,6,7-trimethyloct-6-en-2-one C. Each of the ketones of part B is reacted with the carbanion of diethyl 3-ethoxycarbonyl-2-methylprop- 2-enyl phosphonate acccording to procedures described above to prepare the respective tri-unsaturated ester i.e.

ethyl 3,5,7,l l-tetramethyldodeca-2,4,lO-trienoate ethyl 3,5,7,l l-tetramethyltrideca-2,4, l 0-trienoate ethyl 3,5,7-trimethyl-l l-ethyltrideca-2,4, l

trienoate ethyl 3,5,7,10,l l-pentamethyldodeca-2,4.l0-

trienoate ethyl 3,5,7,1 l,l2-pentamethyltrideca-2,4,l l-

trienoate ethyl 3,5,6,8,9-pentamethyldeca-2,4,8-trienoate ethyl 3,5,6,9-tetramethyldeca-2,4,8-trienoate ethyl 3,5,7,9,lO-pentamethylundeca-2,4,9-trienoate ethyl 3,5,7,lO-tetramethylundeca-2,4,9-trienoate ethyl 3,5,6. lO-tetramethyIundeca-2,4,9-trien0ate ethyl 3,5,6,9,l0-pentamethylundeca-2,4,9-trienoate EXAMPLE 43 A. Each of the ketones of part B of Example 42 is reacted with the carbanion of diethyl 3-ethoxycarbonyll,2-dimethylprop-2-enylphosphonate to prepare the respective trienoate i.e.

ethyl 3,4,5,7,l l-pcntamethyldodeca-2,4,l0-

trienoate ethyl 3,4,5,7,l l-pentamethyltrideca-2,4,IO-trienoate ethyl 3,4,5,7-tetramethyl-l l-ethyltrideca-2,4,l0-

trienoate ethyl 2.4.5 ,7, l 0-1 l-hexamethyldodeca-2,4,10-

trienoate ethyl .45.7.1 l.l2-hexamethyltrideca-2,4,l l-

trienoate ethyl 3,4,5,6.8,9-hexamethyldeca-2,4.8-trienoate ethyl 3.4,5.6,9-pentamethyldeca-2,4,8-tricnoate ethyl 3.45.7.9, l (l-hexamcthylundeca-2.4,9-trienoate thylprop-Z-enyl phosphonate to prepare the respective trienoate, i.e.

ethyl 3 ,4,7,l 1-tetramethyltrideca-2,4, l O-trienoate ethyl 3 ,4,1 l-trimethyl-7-ethyltrideca-2,4, l

trienoate ethyl 3,4-dimethyl-7,l l-diethyltrideca-2,4, l O- trienoate ethyl 3,4,8, 1 Z-tetramethyltrideca-Z,4,l l-trienoate ethyl 3 ,4,7, l 0-tetramethylundeca-2 ,4,9-trienoate ethyl 3 ,4,7 ,10-tetramethyldodeca-2,4,9-trienoate ethyl 3 ,4,6,10-tetramethylundeca-2,4,9-trienoate By use of the procedure of part B of this example, other aldehydes of formula I (R is hydrogen are converted into the respective ester of formula B wherein R is hydrogen and R is methyl or other lower alkyl. Similarly following the procedure of part A of this example, other ketones of formula I (R is lower alkyl) are converted into esters of formula B wherein each of R and R is lower alkyl. Using the process of part C of Example 42 other esters of the present invention of formula B wherein R is hydrogen and R is methyl or other lower alkyl can be prepared using a ketone of formula I (R is lower alkyl) as the precursor.

C. Each of the esters of this example and Example 42 can be hydrolyzed to the free acid according to the procedure of Example 3 or 33. The acid or acid chloride can be reacted with an alcohol such as isopropanol, tbutanol, benzyl alcohol, and the like to prepare the other esters of the present invention.

EXAMPLE 44 Following the process of Example 35, ll-methoxy- 3,7,1l-trimethyldodeca-2,4-dienoic acid is esterified using each of cyclohexanol, n-propanol, i-butanol, benzyl alcohol, phenol n-hexanol, 3,3-dimethylpentan-lol, 2-methylpentan-1-ol, hexan-2-ol, 3-methylpentanl-ol, p-ethylphenol, B-phenylethanol, 2-fluoroethanol, 2,2-dichloroethanol, 2-chloropropan-l-ol, 2,2,2- trichloroethanol and and p-methylthiophenol to prepare the respective ester.

cyclohexyl l l-methoxy-3,7,l l-trimethyldodeca-2,4-

dienoate n-propyl dienoate i-butyl dienoate benzyl dienoate phenyl dienoate n-hexyl dienoate 3', 3-dimethylpentyl l l-methoxy-3,7,l l-trimethyldodeca-2,4-dienoate 2'-methylpentyl dodeca-2,4-dienoate hexan-2-yl l l-methoxy-3,7,l l-trimethyldodeca-2,4-

dienoate 3-methylpentyl dodeca-2,4-dienoate p-ethylphenyl 1 l-methoxy-3 ,7,l l-trimethyldodeca- 4 2,4-dienoate B-phenylethyl 1 1-methoxy-3,7,l l-trimethyldodeca- 2,4-dienoate l l-methoxy-3 ,7,l l-trimethyldodeca-2,4-

1 l-methoxy-3 ,7,l l-trimethyldodeca-2,4-

1 l-methoxy-3 ,7,l l-trimethyldodeca-2,4-

l l-methoxy-3 ,7,l l-trimethyldodeca-2,4-

l l-methoxy-3 ,7,l l-trimethyldodeca-2,4-

l l-methoxy-3,'7,l l-trimethyll 1-methoxy-3,7,l l-trimethyl- 2-fluoroethyl l l-methoxy-3,7,l l-trimethyldodeca- 2,4-dienoate 2',2, -dichloroethyl ll-methoxy-3,7,ll-trimethyldodeca-2,4-dienoate,

2'-chloropropyl dodeca-2,4-dienoate 2,2,2'-trichloroethyl l 1-methoxy-3,7,1 l-trimethyldodeca-2,4-dienoate p-methylthiophenyl dodeca-2,4-dienoate EXAMPLE 45 To a solution of 0.5 g. of trans, trans ll-methoxy- 3,7,11-trimethyldodeca-2,4-dienoic acid in 15 ml. of benzene is added, with stirring, an equivalent amount of potassium hydride. The mixture is stirred at room temperature for about 2 hours and then evaporated to give potassium 1 l-methoxy-3,7,1 l-trimethyldodeca- 2,4-dienoate.

In place of KH, there can be used KOH, NaOH, and the like to form the corresponding salt.

EXAMPLE 46 Methanol is added to the terminal bond of ethyl 3,4,- 7,ll-tetramethyldodeca-2,4,lO-trienoate using the process of Example 23 or 29 to give ethyl 1 l-methoxy- 3,4,7,l l-tetramethyldodeca-2,4-dienoate. In the same manner, water is added to give ethyl ll-hydroxy- 3 ,4,7,1 1-tetramethyldodeca-2,4-dienoate. Similarly, there is prepared ethyl ll-methoxy-3,5,7,l ltetramethyldodeca-2,4-dienoate and ethyl l l-hydroxy- 3,5,7,ll-tetramethyldodeca-2,4-dienoate from ethyl 3,5,7,1 1-tetramethyldodeca-2,4,lO-trienoate. The hydrochloride, ethyl l l-chloro-3,4,7,l l-tetramethyldodeca-2,4-dienoate and ethyl ll-chloro-3,5,7,l1- tetramethyldodeca-2,4-dienoate are prepared from the trienoate using the process of Example 39.

EXAMPLE 47 A. To a solution of 1.8 g. of 6,10-dimethylundeca- 3,9-dien-2-one in 20 ml. of ethanol, cooled to 0 by an ice bath is added a suspension of 2.32 g. of mercuric acetate in 50 ml. of ethanol over- 15 minutes. The reaction mixture is stirred for 2- hours and then, with cooling, to 20, 1.22 g. of potassium hydroxidejn 20 ml. of ethanol is added. Then 0.139 g. of sodium borohydride is added in small portions and stirring continued for 30 minutes at 20. The solution is decanted, then concentrated to half volume, diluted with ml. of water and extracted with ether (3 X 50). The ethereal phase is washed with water, dried over magnesium sulfate and the crude product chromatographed on silica to yield lO-ethoxy-6,lO-dimethylandec-3-en-2-one.

The process of this example is repeated using each of the compounds under column VI as the starting material to prepare the respective ethoxy substituted compound under column XVI.

XVI

10-ethoxy-6,lO-dimethyldodec-3-en-2-one lO-ethoxy-6-methyll O-ethyldodec-3-en-2-one l0-ethoxy-6,lO-diethyldodec3-en-2-one l l-ethoxy-7,l l-dimethyldodec-3-en-2-one 9-ethoxy-6,9-dimethyldec-3-en-2-one 9-ethoxy-6,9-dimethylundec-3-en-2-one 9-ethoxy-5,9-dimethyldec-3-en-2-one Following the process of Example l3, lO-ethoxy- 6,lO-dimethylundec-3-en-2-one is converted into methyl 1 l-ethoxy-3,7,l l-trimethyldodeca-2,4-

l l-methoxy-3 ,7 ,1 l-trimethyll l-methoxy-3,7,l l -trimethyldienoate. Reaction of lO-ethoxy-6,10-dimethylundec- 3-en-2-one with the carbanion of diethyl carboethoxymethylphosphonate yields ethyl 11- ethoxy-3 ,7 ,l l-trimethyldodeca-Z ,4-dienoate.

By using other alcohols in the process of this example in lieu of ethanol, such as methanol, etc., the respective ethers are obtained, e.g., l-methoxy-6, IO-dimethylundec-3-en-2-one.

B. The process of part (A) is repeated using the starting material 3,7-dimethyloct-6-en-l-al and each of the aldehydes under column I or the acetal thereof to prepare the respective compounds under column XVII.

XVII

7-ethoxy-3,7-dimethyloctan- 1 -al 7-ethoxy-3,7-dimethylnonan-l-al 7-ethoxy-3-ethyl-7-methylnonan- 1 -al 7-ethoxy-3,7-diethylnonan-l-al 8-ethoxy-4,8-dimethylnonan- 1 -al 6-etho xy-3 ,6-dimethylheptan- 1 -al 6-ethoxy-3 ,6-dimethyloctan- 1 -al 6-ethoxy-2,6-dimethylheptan- 1 -al Using 7-ethoxy-3,7-dimethy1octan- 1 -al as the starting material in the process of either Example 9, or 11, there is prepared 10-ethoxy-6,l0-dimethylundec-3-en- 2-one.

EXAMPLE 49 To a solution of 2 g. of methyl 3,7,11-trimethyldodeca-2,4,l0-trienoate and ml. of dry ether, at 7 8, is added slowly about 0.4 g. of lithium aluminum hydride in dry ether. The mixture is allowed to stand about one hour after addition is complete and then allowed to warm up to room temperature. Then 2.5 ml. of acetic acid is added. The mixture is then washed with ice water and the organic phase separated, which is dried over magnesium sulfate and evaporated to yield 3,7 ,l l-trimethyldodeca-2,4, l O-trien- 1 -ol.

By use of the process of this example, each of the esters under Column II or VII is reduced to prepare the respective allylic alcohol, i.e.,

3 ,7 ,l l-trimethyltrideca-2,4,10-trien-1-ol,

3 ,1 1-dimethyl-7-ethyltrideca-2,4, l O-trienl-ol,

7 ,1 l-diethyl-3-methyltrideca-2,4, l O-trien- 1 -ol,

3 ,8 l 2-trimethyltrideca-2,4,l l-trien- 1 -ol,

3 ,7 ,10-trimethylundeca-2,4,9-trien-1-ol,

3,7,lO-trimethyldodeca-2,4,9,-trien-l-ol,

3 ,6, l O-trimethylundeca-2,4,9-trien- 1 -ol,

Each of:

methyl trienoate, methyl dienoate, methyl dienoate, methyl 3,5,7,11-tetramethyldodeca-2,4,lO-trienoate, methyl 3,4,7,1 l-tetramethyldodeca-2,4, IO-trienoate,

3,7,10,l l-tetramethyldodeca-2,4,10-

1 1-methoxy-3,7,1 l-trimethyldodeca-2,4

l0-methoxy-2,7, lO-trimethylundeca-Z ,4-

methyl 3,5,7,l0,l 1 pentamethyldodeca-2,4,l0-

trienoate,

methyl 1 l-ethoxy-3,7,l 1-trimethy1dodeca-2,4-

dienoate and methyl 1 1-chloro-3,7,l 1-trimethyldodeca-2 ,4-

dienoate is reduced using lithiumaluminum hydride to the respective C-l alcohol, i.e.,

3,7,10,1 l-tetramethyldodeca-2,4, 1 O-trien- 1 -ol, 1 l-methoxy-3,7,l l-trimethyldodeca-2,4-dien-l-ol, lO-methoxy-3 ,7, l O-trimethylundeca-Z,4-dien- 1 -ol 3,5,7,l l-tetramethyldodeca-2,4,10-trien-l-ol,

3,4,7,1 l tetramethyldodeca-2,4,IO-trien-l-ol,

3 ,5 ,7,10, 1 l-pentamethyldodeca-2,4, l O-trien- 1 -ol,

1 1-ethoxy-3 ,7,1 l-trimethyldodeca-2,4-dien- 1 -ol and l l-chloro-3,7,l 1-trimethyldodeca-2,4-dien- 1 -ol.

EXAMPLE 50 To a mixture 4 g. of 3,7,1l-trimethyldodeca-2,4,l0- trien-l-ol and 25 ml. of benzene at 0 is added a solution of 5 ml. of phosphorus tribromide in 18 ml. of benzene over about 15 minutes. The mixture is stirred at 0 for 1 hour. The mixture is then poured onto ice and extracted with pentane. The organic phase is washed with aqueous sodium bicarbonate, water and then brine, dried over magnesium sulfate and evaporated to yield l-brom0-3 ,7,l l-trimethyldodeca-2,4,10-triene.

The process of this example is repeated using each of the alcohols of Example 49 to prepare the respective bromide, i.e.,

3,7,1 1-trimethyltrideca-2,4,IO-trienyl bromide,

3 ,l l-dimethyl-7-ethyltrideca-2,4, l O-trienyl bromide,

'7 ,l 1-diethyl-3-methyltrideca-2,4, l O-trienyl bromide,

3 ,8,12-trimethyltrideca-2,4,l l-trienyl bromide,

3 ,7 ,10-trimethylundeca-2,4,9-trienyl bromide,

3,7 l O-trimethyldodeca-2,4,9-trienyl bromide,

3 ,6,10-trimethylundeca-2,4,9-trienyl bromide,

3,7,10,l 1-tetramethyldodeca-2,4,10-trienyl bromide,

l l-methoxy-3,7,l l-trimethyldodeca-2,4-dienyl bromide,

l0-methoxy-3,7,10-trimethylundeca-Z,4-dienyl bromide,

3,6,7,l 1-tetramethyldodeca-2,4,lO-trienyl bromide, 3,4,7,1 l-tetramethyldodeca-2,4, lO-trienyl bromide,

3,5,7, 10,1 1-pentamethyldodeca-2,4, l O-trienyl bromide,

l 1-ethoxy-3,7,l1-trimethyldodeca-2,4-dienyl bromide,

l 1-chloro-3,7,1l-trimethyldodeca-2,4-dienyl bromide.

By repeating the process of this example using phosphorus trichloride in place of phosphorus tribromide, the novel allylic chlorides are prepared, i.e., 3,7,11- trimethyldodeca-2,4,lO-trienyl chloride, 3,7,11- trimethyltrideca-2,4, 1 O-trienyl chloride, 3,1 ldimethyl-7-ethyltrideca-2,4,IO-trienyl chloride, etc.

EXAMPLE 51 Ten grams of l-bromo-3,7,1l-trimethyldodeca- 2,4,lO-triene is mixed with 50 ml. of benzene, cooled to 5-l0 and saturated with ammonia. The resulting mixture is stirred for 4 hours allowing the temperature to rise to about 20 while maintaining dry conditions. The mixture is washed with dilute sodium hydroxide and then evaporated under reduced pressure to yield 3 ,7,1 l-trimethyldodeca-2 ,4, lO-trienylamine.

By repeating the process of this example using the allylic bromides or chlorides of Example 50, the respective amines are prepared, e.g., 3,7,1 l-trimethyltrideca- 2,4, 1 O-trienylamine, 3 ,1 l-dimethyl-7-ethyltrideca- 2,4,10-trienylamine, l l-methoxy-3 ,7 ,1 l-trimethyldodeca-2,4-dienylamine, l0-methoxy-3 ,7, l O- trimethylundeca-2,4-dienylamine, l 1-chloro-3,7,l 1- trimethyldodeca-Z,4-dienylamine, etc.

EXAMPLE 52 Five grams of l bromo-3,7,l l-trimethyldodeca- 2,4,l0-triene in 25 ml. of benzene is mixed with 4 g. of diethylamine and the mixture stirred for about 3 hours.

Methylene chloride (50 ml.) is added and the mixture washed with dilute sodium hydroxide and then water and evaporated to yield N,N-diethyl 3,7,1 l-trimethyldodeca-2,4,IO-trienylamine.

The process of this example is repeated using either the bromides or chloride of Example 50 as the starting material to prepare the respective N,N-diethyl amine, e.g., N,N-diethyl 3,7,1 l-trimethyltrideca-2,4,ltrienylamine, N,N-diethyl 3,1l-dimethyl-7-ethyltrideca-2,4,lO-trienylamine, N,N-diethyl l l-methoxy- 3,7,11trimethyldodeca-2,4-dienylamine, N,N-diethyl lO-methoxy-2,7 l 0-trimethylundeca-2,4-dienylamine, N,N-diethyl ll-chloro 3,7,1l-trimethyldodeca-2,4- dienylamine, N,N-diethyl 3,7,l0-trimethylundeca-2,4- dienyl amine, etc. 3

Other amines of the present invention of formula A and B are prepared by use of the foregoing procedure using an amine of the formula:

such as dimethylamine, ethylamine, methylamine, pyrrolidine, morpholine, 4-ethylpiperazine, and the like, in place of diehtylamine, Thus, there is prepared N,N- dimethyl 3,7,1l-trimethyldodeca-2,4,IO-trienylamine, N,N-dimethyl 3,7,1 1-trimethyltrideca-2,4,l0- trienylamine, N-ethyl 3,7,1l-trimethyldodeca-2,4,l0- trienylamine, N-ethyl 3,7,1 l-trimethyltrideca-2,4,l0- trienylamine, etc.

Although not intending to be limited by a theoretical explanation, the effectiveness of the compounds of the present invention to control insects is attributed to the property of these novel compounds to mimic the activity of juvenile hormone. While the methods of applying and carriers for conventional insecticides are usually adaptable to the practical use of the compounds of the present invention, the mechanism of action of these novel compounds is unlike that of conventional insecticides. Whereas conventional insecticides are dependent upon direct knock-down effect, toxity effect or paralyzing effect, the compounds of this invention achieve control by reason of their ability to inhibit metamorphosis, inhibit reproduction due to abnormal development, break diapause at an unfavorable time, or as a direct insecticide, particularly at the embryo stage and larvae stage. Treatment of insects in accordance with the present invention can be achieved via ingestion of the active compound in the normal food of the insect and by topical application, that is by contact of the epidermis of the insect as by spraying the insect and habitat of the insect or exposure to vapors of the active compound which penetrate into the insect.

The compounds of the present invention can be used in conjunction with other juvenile hormone active substances and conventional insecticides to obtain a broad specturm of activity or to provide more immediate effect on very heterogeneous populations. Typical insecticides which may be combined with the compounds of the present invention are Malathion, Sevin, Vapona, Abate, synthetic and natural pyrethrins, and the like, and usually within the ratio of between 10:1 to 1:10, by weight.

EXAMPLE 53 To a solution of 6.2 g. of ethyl ll-methoxy-3,7,l ltrimethyldodeca-2,4-dienoate in ml. of dry ether is added 3.2 ml. of lithium aluminum hydride (3.9M) in ether slowly, at 78, with stirring, under argon. The mixture is stirred for 2 hours at 78 and then warmed to about 50". After 1 hour, the mixture is warmed slowly to about 10" over 4 hours. Then there is added 0.5 ml. of water, 0.5 ml.'of 15% sodium hydroxide and 1.5 ml. of water. The mixture is then poured into water, washed with water and brine, dried over magnesium sulfate and evaporated to yield 1l-methoxy-3,7,l ltrimethyldodeca-2,4-dien- 1 ol.

EXAMPLE 54 To a solution of 1.90 g. of 1l-methoxy-3,7,l 1- trimethyldodeca-2,4-dien-l-ol in 20 ml. of ether is added a solution of 0.80 g. of phosphorus tribromide in 10 ml. of ether, under nitrogen, with stirring at 50". The reaction mixture is stirred for three hours at 60 to 40 and then poured into ice water, which is then washed with sodium bicarbonate solution water and brine, dried over calcium sulfate and evaporated under reduced pressure to yield 1 l-methoxy-3,7,l ltrimethyldodeca-2,4-dienyl bromide.

EXAMPLE 55 To 250 ml. of anhydrous pyridine, cooled in an icebath, is added 35.2 g. of p-toluenesulfonyl chloride. When the sulfonyl chloride is dissolved, 34 g. of 3,7,1 1- trimethyldodeca-2,4,10-trien-1-ol is added with 210 ml. of anhydrous pyridine. The reaction mixture is stirred at about 5-l0 for 24 hours. Then 40 ml. of cold water is added and the mixture stirred for 1 hour at ice temperature. The mixture is extracted with pentane. The pentane extracts are washed with 10% HCl and water, dried over potassium sulfate/potassium carbonate and concentrated under reduced pressure. The concentrate is taken up in 50 ml. of dry acetone and added to a solution of 36 g. of dry sodium iodide in 150 ml. of dry acetone. The reaction mixture is stirred at room temperature for about 20 hours and then filtered. The filtrate is concentrated and taken up in pentane. The pentane solution is washed with water, dried over sodium sulfate and evaporated to yield 3,7,1 1- trimethyldodeca-2,4,10-trienyl iodide, which can be purified by chromatography.

EXAMPLE 56 A mixture of 33 g. of l-bromo-3.7,l l-trimethyldodeca-2,4,lO-triene and ml. of dry ethylene glycol is slowly added with stirring, to a suspension of l 1.5 g. of potassium fluoride in 30 ml. of dry ethylene glycol and heated to about ,under an inert atmosphere. When addition is completed, the reaction mixture is stirred for about an additional 16 hours while maintaining the temperature at 120.Then the mixture is cooled and 200 ml. of ether added. The mixture is washed throughly with water and the ether phase dried over so- 25 dium sulfate and solvent evaporated under reduced pressure to yield l-fluoro-3,7,l l-trimethyldodeca- 2,4,l-triene.

The same compound can be prepared by using an equivalent amount of silver fluoride in place of potassium fluoride.

EXAMPLE 57 Using the procedure of Example 55, each of 11- methoxy3,7,1 1-trimethyldodeca-2,4-dien-1-ol, l 1- ethoxy-3,7,1 1-trimethyldodeca-2,4-dien- 1 -ol, 3,7,10- trimethy1undeca-2,4,9-trien-l-ol, l0-methoxy-3,7,10- trimethylundeca-2,4-dien-1-01, 1 l-methoxy-3,7,10,1 ltetramethyldodeca-2,4-dien-1-o1, and 3,7,10,1 1- tetramethyldodeca-2,4,10-trien-1-ol is converted into the iodide, that is l l-methoxy-3,7,1 l-trimethyldodeca- 2,4-dienyl iodide, 1 1-ethoxy-3,7,1 l-trimethyldodeca- 2,4-dienyl iodide, 3,7,10-trimethylundeca-2,4,9-trieny1 iodide, l0-methoxy-3,7,l 0-trimethylundeca-2,4-dienyl iodide, 1 1-methoxy-3,7,l0,1 1-tetramethy1dodeca-2,4- dienyl iodide and 3,7,10,l 1-tetramethyldodeca-2,4,10- trienyl iodide.

EXAMPLE 58 By using the process of Example 56, each of 11- methoxy-3,7,l1-trimethyldodeca-2,4-dienyl fluoride, 1 l-methoxy-3 ,7, l 0,1 1-tetramethyldodeca-2,4-dienyl fluoride, l0-methoxy-3 ,7, l 0-trimethylundeca-2,4-

dienyl fluoride, 3,7,10,1l-tetramethyldodeca-2,4,10- 3 trienyl fluoride, 3,7,lO-trimethylundeca-2,4,9-trienyl fluoride, and 3,7,1 1-trimethyltrideca-2,4,IO-trienyl fluoride is prepared from the respective bromide precursor, l l-methoxy-3,7,1 1-trimethyldodeca-2,4-dieny1 bromide, l l-methoxy-3,7,10,1 l-tetramethyldodeca- 2,4-dienyl bromide, lO-methoxy-3,7,10-trimethylundeca-2,4-dieny1 bromide, 3,7,l0,l l-tetramethyldodeca-2,4, 10trienyl bromide, 3 ,7 1 O-trimethylundeca-2,4,lO-trienyl bromide, and 3,7,1 l-trimethyltrideca-2,4,l0-trieny1 bromide.

What is claimed is:

1. A compound selected from those of the following formula:

trienylfluoride, according to claim 1. 

1. A COMPOUND SELECTED FROM THOSE OF THE FOLLOWING FORMULA:
 2. A compound according to claim 1 wherein X is bromo or chloro and each of R2 and R3 is methyl.
 3. A compound according to claim 2 wherein R14 is hydrogen.
 4. The compound, 3,7,11-trimethyldodeca-2,4,10-trienyl chloride, according to claim
 3. 5. The compound, 3,7,11-trimethyldodeca-2,4,10-trienyl bromide, according to claim
 3. 6. The compound, 3,7,11-trimethyldodeca-2,4,10-trienyl iodide, according to claim
 1. 7. The compound, 3,7,11-trimethyldodeca-2,4,10-trienyl fluoride, according to claim
 1. 